BR112019021299A2 - soft polypropylene composition with enhanced properties - Google Patents

Abstract

it is a polypropylene composition with improved low temperature impact, low voltage module and low gel content, as well as its manufacture and use and articles produced from the innovative composition.

Description

COMPOSITION OF SOFT POLYPROPYLENE WITH ENHANCED PROPERTIES

[0001] The present invention relates to the polypropylene composition with improved low temperature impact, low voltage module and low gel content, as well as its manufacture and use and to articles produced from the innovative composition.

[0002] Polymers, like polypropylene, are increasingly used in different complex applications. At the same time, there is an ongoing search for custom polymers that meet the requirements of these applications.

[0003] For example, heterophasic propylene copolymers (HECOs or RAHECOs) are already widely used in the industry for various applications. Such HECOs or RAHECOs comprise a matrix that is either a propylene homopolymer (HECOs) or a random propylene copolymer (RAHECOs) in which an elastomeric copolymer is dispersed (rubber phase). In this way, the polypropylene matrix contains dispersed inclusions (finely) that are not part of the matrix and said inclusions contain the elastomeric copolymer. The term inclusion, therefore, indicates that the matrix and inclusion form different phases within the heterophasic system, in which said inclusions are, for example, visible by high resolution microscopy, such as electron microscopy or atomic force microscopy, or be identified by dynamic mechanical thermal analysis (DMTA). Specifically in DMTA, the presence of a multi-phase structure can be identified by

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2/69 presence of at least two different glass transition temperatures.

[0004] Soft heterophasic propylene copolymers are also widely used in various fields of application, such as sheets, soft-touch products for cars, medical tubes or bags, foaming, tiles, bitumen modification, etc. However, due to the nature of the soft heterophasic propylene copolymers, the low temperature impact is insufficient due to the relatively high Tg of the rubber phase (for example, around -25 ° C to -50 ° C). This property, therefore, needs to be further improved. One way is to mix these materials with extra rubber materials, such as styrene block copolymer or polyethylene plastomers, etc. In this document, however, the improvement is still limited due to the factor that the issue of compatibility between rubber external and the matrix cannot be easily solved.

[0005] An additional way to modify the soft heterophasic propylene copolymers is by grafting. However, heterophasic propylene copolymers are particularly sensitive to degradation, in particular, in combination with peroxides, which limits the possibilities for graft modification.

[0006] In view of the above difficulties, there is still a desire to supply materials that do not have one or more of the mentioned disadvantages, in particular, flexible, soft materials that have desired mechanical and chemical properties, such as a low gel content, and softness easily adjustable.

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[0007] Either development to find suitable soft heterophasic propylene copolymers with the desired property profile has been suggested in the past.

[0008] EP 2048185 describes soft PP compositions with a soft feel, wherein said compositions comprise (A) a polypropylene, (B) an elastomeric ethylene copolymer and a C3-C8 α-olefin comonomer, and (C) a C2-C8 alkyl ethylene acrylate copolymer, wherein the composition has a gel content of 0.25 to 1.00% by weight determined as the insoluble fraction of hot xylene, wherein the polypropylene (A) it can be the matrix of a heterophasic propylene copolymer (RAHECO) and the elastomeric copolymer (B) is an amorphous part of said heterophasic propylene copolymer (RAHECO).

[0009] It is preferred that said composition additionally comprises units (D) derived from at least bifunctional unsaturated monomer (or monomers) (D ') and / or at least multifunctional unsaturated low molecular weight polymer (or polymers) (D). The chemical nature of component (C) limits the practical applicability of the respective compositions, and the examples demonstrate the practical need for component (D), generating additional process complexity.

[0010] EP 1564231 A1 refers to the process of grafting monomers into polyolefins in the presence of organic peroxides, in which the monomer (or monomers) and organic peroxide were absorbed into a carrier polymer which, under the conditions of grafting, is subjected to chain splitting, preferably crosslinking in the presence of organic peroxides. According to this patent application,

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4/69 the described grafting process allows to obtain grafted polyolefin compounds, modified by impact with improved extrusion capacity, heat stability and reduced gels or imperfections.

[0011] The impact-modified grafted polyolefins are obtained from ethylene polymer or copolymer (A), in which an impact modified copolymer (B) and product (C) are a propylene polymer or copolymer to which it has been incorporated organic peroxide and a polar monomer and antioxidants.

[0012] As suitable impact modifiers (B), among others, copolymer and / or a terpolymer containing styrene / butadiene / styrene (SBS) blocks, styrene / ethylene-butene / styrene blocks (SEBS) or styrene blocks / isoprene / styrene (SIS) or its hydrogenated or partially hydrogenated equivalents are mentioned, while, in the examples, polymer (B) is a pelleted ethylene-propylene copolymer.

[0013] The only measured property was the adhesion to aluminum foil.

[0014] Regardless, no soft heterophasic propylene copolymer composition has been developed so far, which simultaneously shows improved low temperature impact, low stress module and low gel content and is easily obtainable by an effective grafting process.

[0015] Consequently, it is the aim of the present invention to provide such a composition of soft heterophasic propylene copolymers, which meets all the requirements mentioned above.

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[0016] The finding of the present invention is that heterophasic propylene copolymers must be grafted with a specific styrene-based elastomer in order to achieve soft heterophasic propylene copolymer compositions that meet all the requirements mentioned above.

Summary of the Invention

[0017] Thus, the present invention is related to the composition of heterophasic propylene copolymer

grafted, which comprises (A) 30.0 at 95.0% by weight in a copolymer in polypropylene heterophasic that has an flow rate in fusion (MFR 230 ° C / 2.16 kg, IS01133) in 0.1 to 100 g / 10 min

comprising (al) a matrix (M) which is a homo- or copolymer of crystalline polypropylene and (a2) and elastomeric copolymer (E) dispersed in said matrix (M) (B) 5.0 to 70.0% by weight of a styrene-based elastomer that is an unsaturated styrene block copolymer that contains at least one diene comonomer and that has a styrene content of 5.0 to 50.0% by weight measured by infrared transform spectroscopy Fourier (FTIR), and in which the styrene-based elastomer (B) is grafted into the heterophasic polypropylene copolymer (A).

[0018] Surprisingly, it has been found that such grafted heterophasic polypropylene copolymer compositions have superior properties compared to non-grafted compositions (see table 2). For example, such a polypropylene copolymer composition

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6/69 heterophasic grafted has a low voltage module, as well as high impact resistance, especially at low temperatures.

[0019] In addition, the grafted heterophasic polypropylene copolymer composition has a low amount of gels, which is measured as the insoluble fraction in p-xylene at 25 ° C (fraction XCI).

[0020] In a further embodiment, the present invention relates to a process for producing the grafted heterophasic polypropylene copolymer composition, in which the process is a reactive fusion modification process, which comprises the steps of

i) mixing component (A), the heterophasic polypropylene copolymer with component (B), the styrene-based elastomer and a thermal decomposition free radical forming compound (C) and ii) extruding said mixture.

[0021] In an additional embodiment, the present invention relates to the use of the grafted heterophasic polypropylene copolymer composition to produce extruded films or tubes, injection molded or blow molded articles, and articles comprising the polypropylene copolymer composition. grafted heterophasic.

[0022] Especially such articles are medical tubes or bags that comprise more than 90% by weight of the grafted heterophasic polypropylene copolymer composition.

Detailed Description

[0023] In the following, the individual components are defined in more detail.

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[0024] The grafted heterophasic propylene copolymer composition according to the present invention comprises (A) 30.0 to 95.0% by weight of a heterophasic polypropylene copolymer which has a melt flow rate (MFR 230 ° C / 2 , 16 kg, IS01133) from 0.1 to 100 g / 10min which comprises and

(B) 5.0 to 70.0% by weight of a styrene-based elastomer which is an unsaturated styrene block copolymer that contains at least one comonomer selected from butadiene and isoprene and which has a styrene content of 5.0 to 50.0% by weight, in which the styrene-based elastomer (B) is grafted onto the heterophasic polypropylene copolymer (A).

[0025] The terms heterophasic polypropylene copolymer, base heterophasic polypropylene copolymer used in this document have the same meaning and are thus interchangeable. Thus, these terms represent the non-grafted copolymer, that is, without the styrene-based elastomer.

[0026] The term grafted heterophasic propylene copolymer composition used herein means the composition comprising the heterophasic propylene copolymer in which the styrene-based elastomer is grafted.

Component (A): basic heterophasic polypropylene copolymer

[0027] The base heterophasic polypropylene copolymer comprises at least

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8/69 (al) a matrix (M) which is a homo- or copolymer of crystalline polypropylene and (a2) and elastomeric copolymer (E) dispersed in said matrix (M).

[0028] The term heterophasic polypropylene copolymer used in this document represents copolymers consisting of a matrix resin, which is a homo- or copolymer of crystalline polypropylene and an elastomeric, i.e., predominantly amorphous (E) copolymer dispersed in said resin matrix, as defined in more detail below.

[0029] Optionally, it further comprises component (a3) which is a fraction of crystalline copolymer of ethylene with propylene or with a CH2 = CHR alpha-olefin, and / or (a4) a nucleating agent.

[0030] In the present invention, the term matrix must be interpreted in its commonly accepted meaning, that is, it refers to a continuous phase (in the present invention, a continuous polymer phase) in which distinct or isolated particles as particles of rubber can be dispersed. The crystalline propylene polymer is present in such an amount that it forms a continuous phase that can act as a matrix.

[0031] Furthermore, the terms elastomeric copolymer, dispersed phase and rubber phase represent the same, that is, they are interchangeable.

Ad (al) component:

[0032] Component (al) of the particular heterophasic polypropylene copolymer is a homo- or copolymer of

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9/69 crystalline isotactic propylene that forms the matrix of the heterophasic polypropylene copolymer.

[0033] The term homopolymer used in the present invention refers to a polypropylene that consists substantially, that is, at least 97.0% by weight, preferably at least 98.0% by weight, more preferably, at least at least 99.0% by weight, even more preferably, at least 99.8% by weight of propylene units. In a preferred embodiment, only propylene units in the propylene homopolymer are detectable.

[0034] The propylene homopolymer matrix is isotactic that has a high pentad concentration, that is, greater than 96.0 mol%, as a pentent concentration of at least 96.3 mol%. The penny concentration is preferably from 96.5 mol% to 99.9% and, more preferably, 96.7 mol% to 99.8%.

[0035] The matrix can also be a propylene copolymer, that is, a random propylene copolymer.

[0036] The random propylene copolymer comprises monomers copolymerizable with propylene, for example, comonomers, such as ethylene and / or C4 to Cs α-olefins, in particular ethylene and / or C4 to Ce α-olefins, for example 1- butene and / or 1-hexene. Preferably, the random propylene copolymer comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene. More specifically, the random propylene copolymer comprises - separated from propylene - derivable units of ethylene and / or 1-butene. In a preferred mode, the

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10/69 random propylene copolymer comprises derivatives of ethylene and propylene only.

[0037] The random propylene copolymer is portrayed by a moderate comonomer content. Consequently, the comonomer content of the random propylene copolymer is in the range of 1.0 to 12.0% by weight, preferably in the range of 2.0 to 10.0% by weight and, more preferably, in the range of 3.0 to 8.0% by weight.

[0038] The propylene homo- or copolymer matrix has a melting flow rate MFR2 (ISO 1133; 230 ° C; 2.16 kg) in the range of 0.5 to 100.0 g / 10 min, preferably , in the range of 1.0 to 50.0 g / 10 min, more preferably, in the range of 1.5 to 20.0 g / 10 min and, even more preferably, 2.0 to 10.0 g / 10 min .

[0039] The MFR2 of matrix is called rate in melt flow matrix (MFR _m ). [0040] Furthermore, is preferential what The amount in soluble xylene homogen matrix or copolymer in

propylene is in a defined range. Soluble xylene is the part of the polymer soluble in cold xylene determined by dissolving it in boiling xylene and letting the insoluble part crystallize from the cooling solution (determined at 25 ° C according to ISO 16152). The fraction of soluble xylene contains polymer chains of low stereo regularity and is an indication for the number of non-crystalline areas. Consequently, it is preferred that the fraction of xylene soluble in the propylene homo- or copolymer matrix is in the range of 0.5% by weight to 20.0% by weight, more preferably, in the range of 0.7% by weight to 18.0% by weight. In a modality

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11/69 even more preferred, the fraction of soluble xylene is in the range of 0.8% by weight to 16.0% by weight.

[0041] The propylene homo- or copolymer matrix can be unimodal or multimodal, such as bimodal.

[0042] When the propylene homo- or copolymer matrix phase is unimodal in relation to the molecular weight distribution, it can be prepared in a single stage process, for example, a gas phase or slurry process in a gas phase reactor or slurry. Preferably, a unimodal matrix phase is polymerized as a slurry polymerization. Alternatively, the unimodal matrix can be produced in a multistage process using, at each stage, process conditions that result in similar polymer properties.

[0043] Regarding the definition of unimodal and multimodal, as bimodal, the same is presented in the definition below.

[0044] Where the propylene homo- or copolymer matrix comprises two or more different propylene polymers, where they may be polymers with different monomer production and / or with different molecular weight distributions and / or MFR2. These components can have different or identical tactics and monomer compositions.

Thus, in one embodiment of the present invention, the matrix is unimodal, while, in another embodiment, the matrix (M) is bimodal and consists of two propylene homopolymer fractions, two propylene copolymer fractions or a fraction of homo and a fraction of copolymer.

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[0046] In a preferred embodiment, the component matrix (A) is a random propylene copolymer (RPP). Even more preferably, the component matrix (A) is a random propylene-ethylene copolymer. Ad component (a2):

[0047] Component (a2) the particular heterophasic polypropylene copolymer is the elastomeric copolymer (E), which is a predominantly amorphous (ii) copolymer of ethylene and a C3-C10 a-olefin.

[0048] In this way, the component (a2) is an elastomeric copolymer, which is dispersed in said matrix (M) (i.e., dispersed phase).

[0049] The elastomeric copolymer has an ethylene content, in polymerized form, in the range of 20.0 to 80.0% by weight, preferably in the range of 20.0 to 60.0% by weight and, more preferably , in the range of 20.0 to 50.0% by weight.

[0050] The elastomeric copolymer (E) comprises, especially consists of, ethylene and comonomers copolymerizable with ethylene, for example, comonomers such as propylene and / or C4 to Cio α-olefins, in particular, propylene and / or C4 to Ce α- olefins, for example, 1-butene and / or 1hexene, in polymerized form. Preferably, the elastomeric copolymer comprises, especially consists of, ethylene and comonomers copolymerizable with ethylene from the group consisting of propylene, 1-butene and 1-hexene. More specifically, the elastomeric copolymer (E) comprises separate from ethylene - derivable units of propylene and / or 1-butene. Thus, in an especially preferred embodiment, the elastomeric copolymer (E) comprises derivable units of ethylene and propylene only. IS

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13/69 especially preferred that the random propylene copolymer (R-PP) and the elastomeric copolymer (E) comprise the same comonomers in polymerized form. Consequently, in a specific embodiment, the random propylene copolymer matrix (R-PP) and the elastomeric copolymer (E) comprise only propylene and ethylene, in polymerized form.

[0051] As indicated above, the terms elastomeric copolymer, dispersed phase and rubber phase represent the same, that is, they are interchangeable.

[0052] Like the propylene homo- or copolymer matrix, the dispersed phase can be unimodal or multimodal, such as bimodal.

[0053] In one embodiment, the dispersed phase is unimodal. More particularly, the dispersed phase is preferably unimodal taking into account the intrinsic viscosity and / or the comonomer distribution. Regarding the definition of unimodal and multimodal, as bimodal, it is presented in the definition above.

[0054] Preferably, the dispersed unimodal phase is produced in a reaction stage, more preferably, in a gas phase reactor which comprises, respectively, consists of fractions of a copolymer. Ad component (a3):

[0055] The component (a3), a fraction of crystalline ethylene copolymer of ethylene with an α-olefin having 3 to 10 carbon atoms is optionally present, wherein said fraction is insoluble in xylene at room temperature. [0056] α-olefins with 3 to 10 carbon atoms are, for example, propylene, 1-butene, 1-pentene, 1-hexene, 1 Petition 870190101796, from 10/10/2019, pg. 22/83

14/69 heptene and 1-octene.

[0057] The crystalline ethylene copolymer is a sub-reaction product obtained by preparing the heterophasic polypropylene copolymer. Such a crystalline ethylene copolymer is present as an inclusion in the amorphous phase due to thermodynamic reactions.

[0058] The crystalline ethylene copolymer has a melting temperature Tm2 and a melting enthalpy Hm2, as determined by DSC analysis according to ISO 11357.

[0059] Preferably, Tm2 of the crystalline ethylene copolymer is within the range of 105 ° C to 130 ° C, more preferably, within the range of 110 ° C to 127 ° C and, most preferably, within the range of 112 ° C to 124 ° C.

[0060] Preferably, Hm2 of the crystalline ethylene copolymer is less than 4.0 J / g, more preferably, less than 2.0 J / g and, most preferably, less than 1.0 J / g.

[0061] The crystalline ethylene copolymer is present in an amount of 0.0 to 5.0% by weight

Ad component (a4):

[0062] As an optional component (a-4), a nucleating agent (NA) to promote the isotactic polypropylene α-phase may be present, that is, an anucleation agent.

[0063] The α-nucleating agent is preferably selected from the groups consisting of (i) salts of monocarboxylic acids and polycarboxylic acids, for example, sodium benzoate or aluminum tertbutylbenzoate, and (ii) dibenzylidenosorbitol ( e.g. 1.3: 2.4

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15/69 dibenzylidenosorbitol) and dibenzildenosorbitol derivatives substituted by Cl-C8-alkyl, such as methyldibenzildenosorbitol, etildibenzildenosorbitol or

dimethyldibenzildenosorbitol (e.g. 1.3 2.4

di (methylenzilidene) sorbitol), or substituted nonitol derivatives, such as 1,2,3, -trideoxy-4,6: 5,7-bis-0 - [(4propylphenyl) methylene] -nonitol, and

(iii) salts of phosphoric acid diesters, per

example, 2,2'-methylenebis (4, 6, -di-tert-butylphenyl) sodium phosphate or hydroxy-bis [2,2'-methylene-bis (4,6-di-tbutylphenyl) aluminum phosphate], and (iv) polymeric nucleating agent, and (v) mixtures thereof.

[0064] Such additives are generally commercially available and are described, for example, in Plastic Additives Handbook, 5th edition, 2001 by Hans Zweifel.

[0065] Preferably, the α-nucleating agent is a polymeric nucleating agent, more preferably, a vinylcycloalkane polymer and / or a vinylalkane polymer.

[0066] Said polymeric nucleating agent can to be

introduced into the heterophasic copolymer by mixing with a main batch (MB) together with, for example, a carrier polymer or during the polymerization of the heterophasic propylene copolymer, preferably the polymeric nucleating agent is introduced into the composition by prepolymerization of the catalyst used to prepare part or all of the heterophasic propylene copolymer.

[0067] Any known polymeric nucleating agent can be employed, including vinyl alkane polymers and

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16/69 cycloalkane vinyl.

[0068] A preferred example of such a polymeric nucleating agent is a vinyl polymer, such as a vinyl polymer derived from monomers of the formula

CH ₂ = CH-CHR ¹ R ² where R ¹ and R ² , together with the carbon atom, are attached to, form an optionally substituted aromatic or unsaturated or saturated ring or a fused ring system, in which the ring or chemical portion of fused ring contains from 4 to 20 carbon atoms, preferably 5 to 12 members of aromatic or unsaturated or saturated ring or a fused ring system or independently represents a linear C4-C30 alkane or branched, C4-C20 cycloalkane or C4-C20 aromatic ring. Preferably, R ¹ and R ² , together with atom C, to which they are attached to, form an aromatic or unsaturated or saturated ring of five or six members or independently represent a lower alkyl group comprising 1 to 4 carbon atoms. Preferred vinyl compounds for the preparation of a polymeric nucleating agent to be used according to the present invention are, in particular, cycloalkane vinyl, in particular, cyclohexane vinyl (VCH), cyclopentane vinyl, and vinyl-2-methyl cyclohexane, 3-methyl-1-butene, 3-ethylhexene, 3-methyl-1-pentene, 4-methyl-1-pentene or mixtures thereof. VCH is a particularly preferred monomer. [0069] In that case, the nucleating agent is incorporated into the heterophasic propylene copolymer in the form of a main lot (MB), said polymeric nucleating agent, which is preferably alpha-nucleating agent, with maximum

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17/69 preferably a vinylcycloalkane, such as vinylcyclohexane (VCH), polymer and / or vinylalkane polymer, preferably vinylcyclohexane (VCH), as defined above or below, is preferably present in an amount of not more than 500 ppm, more preferably from 1 to 200 ppm and, even more preferably, from 5 to 100 ppm, based on the weight of the main batch (100% by weight). In this modality, more preferably, said main batch (MB) is present in an amount of not more than 10.0% by weight, more preferably, not more than 5.0% by weight and, most preferably, not more than 3.5% by weight, with the preferred amount of the main batch (MB) which is 1.5 to 3.5% by weight, based on the total amount of the heterophasic propylene copolymer. Most preferably, the main batch (MB) preferably comprises a homopolymer or copolymer, preferably homopolymer, of propylene which has been nucleated according to BNT technology as described below.

[0070] It is preferred that the polymeric nucleating agent is introduced to the heterophasic propylene copolymer during the polymerization process of the heterophasic propylene copolymer. The nucleating agent is preferably introduced into the heterophasic propylene copolymer by first polymerizing the vinyl compound defined above, preferably vinylcycloalkane, as defined above or below, in the presence of a catalyst system comprising a catalyst component preferably a solid Ziegler Natta catalyst component, an optional external donor cocatalyst, and the reaction mixture obtained from the polymer of the

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18/69 vinyl compound, preferably cyclohexane vinyl polymer (VCH), and the catalyst system is then used to produce the heterophasic propylene copolymer. The above incorporation of the polymeric nucleating agent into the heterophasic propylene copolymer during the polymerization of said heterophasic propylene copolymer is referred to herein as BNT technology, as described below.

[0071] The said reaction mixture obtained is, in the present document, called interchangeably below, as a modified catalyst system.

[0072] Preferably, the polymeric nucleating agent is vinylcyclohexane polymer (VCH) which is introduced into the heterophasic propylene copolymer by BNT technology.

[0073] More preferably, in this preferred embodiment, the amount of polymeric nucleating agent, such as vinylcyclohexane (VCH), polymer and / or vinylalkane polymer, more preferably, of vinylcyclohexane polymer (VCH), in the copolymer of heterophasic propylene is not more than 500 ppm, more preferably, from 1 to 200 ppm, most preferably 5 to 100 ppm.

[0074] Regarding the BNT technology, reference is made to international orders WO 99/24478, WO 99/24479 and, particularly, WO 00/68315. According to this technology, a catalyst system, preferably a Ziegler-Natta procatalyst, can be modified by polymerizing a vinyl compound in the presence of the catalyst system, which comprises, in particular, the Ziegler-Natta procatalyst, an external donor it is a

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19/69 cocatalyst, in which the vinyl compound has the formula: CH2 = CH-CHR ¹ R ² as defined above.

[0075] The polymerized vinyl compound acts as an alpha-nucleating agent. The weight ratio between vinyl compound and solid catalyst component in the catalyst modification step is preferably up to 5 (5: 1), preferably up to 3 (3: 1), most preferably 0 , 5 (1: 2) to 2 (2: 1). The most preferred vinyl compound is vinylcyclohexane (VCH).

[0076] When a polymeric nucleating agent is introduced into the heterophasic propylene copolymer during the polymerization process, the amount of nucleating agent present in the heterophasic propylene copolymer is preferably not more than 500 ppm, more preferably, 0.025 at 200 ppm, even more preferably, it is 1 to 100 ppm and, most preferably, it is 5 to 100 ppm, based on the heterophasic propylene copolymer and the nucleating agent, preferably based on the total weight of the propylene copolymer heterophasic including all additives.

Component (A) properties _r the base heterophasic polypropylene copolymer

[0077] The heterophasic polypropylene copolymer of the present invention is further characterized by a total melt flow rate (MFRt) (ISO 1133; 230 ° C; 2.16 kg) in the range of 0.1 to 100.0 g / 10 min, preferably in the range of 1.0 to 80.0 g / 10 min, more preferably, in the range of 2.0 to 60.0 g / 10 min and, even more preferably, in the range of 4.0 at 40.0 g / 10 min.

[0078] Preferably, the final melt flow rate of the

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20/69 heterophasic propylene copolymer is adjusted during the polymerization process. Consequently, the reactor-produced heterophasic propylene copolymer has the melt flow rate as defined above or in the claims. The heterophasic propylene copolymer produced by reactor represents in this document that the melting flow rate of the heterophasic propylene copolymer has not been modified for the purpose of post-treatment. Consequently, in a preferred embodiment, the heterophasic propylene copolymer is not viscorreduced, particularly not viscorreduced with the use of peroxide. Consequently, the melt flow rate is not increased by reducing the chain length of the heterophasic propylene copolymer according to that invention by using peroxide. Thus, it is preferable that the heterophasic propylene copolymer does not contain any peroxide and / or its decomposition product.

[0079] It is also observed that the total content of the ethylene comonomers in the total heterophasic propylene copolymer is preferably moderate.

Consequently, it is preferred that the heterophasic propylene copolymer has a total ethylene comonomer content in the range of 2.5 to 15.0% by weight, preferably in the range of 3.0 to 12.0% in weight and, more preferably, in the range of 4.0 to 10.0% by weight.

[0081] In addition, the polypropylene copolymer

heterophasic inventive has at least any less an first temperature transition glassy Tg (l) is Monday temperature transition glassy Tg (2), on what the said

first glass transition temperature Tg (l) is above

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21/69 of the second glass transition temperature Tg (2). The glass transition temperature Tg is determined by dynamic mechanical analysis (DMTA) according to ISO 6721-7.

[0082] Consequently, it is especially preferred that the heterophasic polypropylene copolymer has a first glass transition temperature Tg (l) in the range of -12 ° C to +4 ° C and / or a second glass transition temperature Tg (2) in the range of -65 ° C to -30 ° C.

[0083] The multi-phase structure of the heterophasic polypropylene copolymer (predominantly amorphous ethylene copolymer dispersed in the matrix) can be identified by the presence of at least two distinct glass transition temperatures. The first highest glass transition temperature (Tg (l)) represents the matrix, that is, the crystalline polypropylene homo- or copolymer, while the first lowest glass transition temperature (Tg (2)) reflects the ethylene copolymer predominantly amorphous of the heterophasic polypropylene copolymer.

[0084] Preferably, the first glass transition temperature Tg (l) is in the range of -8 ° C to +3 ° C, more preferably, in the range of -5 ° C to +2.0 ° C.

[0085] The second glass transition temperature Tg (2) is preferably in the range of -62 ° C to -40 ° C, more preferably in the range of -60 ° C to -45 ° C.

[0086] The amount of the soluble cold xylene fraction (XCS) of the heterophasic propylene copolymer is in the range of 10.0 to 50.0% by weight, taking into account the base heterophasic propylene copolymer, preferably in the range from 10.0 to 40.0% by weight and, more

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22/69 preferably, in the range of 10.0 to 30.0% by weight.

[0087] The viscosity intrinsic ( IV) measure in wake up with ISO 1628-1 (at 135 ° C in decaline ) gives fraction in XCS of propylene copolymer heterophasic it is in the range too much of 1.0 at 5.0 dl / g, from preferably, at banner in 1.2 The 4.0 dl / g and, more preferably, at banner in 1.3 The

3.0 dl / g.

The heterophasic propylene copolymer of the present invention is composed of components (al) and (a2) and optional components (a3) and / or (a4).

[0089] Component (al) is present in an amount of 50.0 to 90.0% by weight, preferably from 52.0 to 88.0% by weight and, more preferably, from 54.0 to 85, 0% by weight.

[0090] Component (a2) is present in an amount of 10.0 to 50.0% by weight, preferably from 12.0 to 48.0% by weight and, more preferably, from 15.0 to 46, 0% by weight.

[0091] Component (a3) is present in an amount from 0 to 5.0, 0% by weight, preferably from 0.0 to 4.0% by weight and, more preferably, from 0.0 to 3.0% in weight.

[0092] Component (a4) is present in an amount of 0.0 to 1.0% by weight, preferably from 0.0 to 0.5% by weight and, more preferably, from 0.0 to 0, 1% by weight.

[0093] If component (a4) is added in the form of a main batch (MB), the quantity of main batch containing component (a4) is up to 10% by weight with respect to the total heterophasic propylene copolymer, preferably up to 5% by weight and, more preferably, in the range of 1.5 to 3.5% by weight based on the total propylene copolymer

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Heterophasic 23/69.

[0094] The sum of fractions (al), (a2), (a3) and (a4) is 100% by weight or less depending on the presence of additional fractions or additives. The weight percent (% by weight) ranges, as used herein, define the amount of each of the fractions or components based on the total heterophasic propylene copolymer according to the present invention. All fractions and components together provide a sum of 100% by weight.

[0095] The heterophasic propylene copolymer according to the present invention, separated from the polymeric components and the nucleating agent (a4), optionally in the form of a main lot (MB), can further comprise non-polymeric components, for example, additives for different purposes. The following additional additives are: hot process and stabilizers, pigments and other coloring agents allowing retention of transparency, antioxidants, antistatic agents, gliding agents, anti-blocking agents, UV stabilizers and acid scavengers.

[0096] Depending on the type of additive, they can be added in an amount of 0.001 to 2.0% by weight, based on the weight of the heterophasic propylene copolymer. Preparation of the heterophasic propylene copolymer

[0097] The heterophasic propylene copolymer according to the present invention can be prepared by any suitable process, including, in particular, blending processes, such as mechanical blending, including mixing and blending process and any combinations thereof, as well as it blends in place during the polymerization process.

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They can be performed by methods known to the skilled person, including batch processes and continuous processes. The heterophasic propylene copolymer according to the invention is preferably prepared by a sequential polymerization process, as described below, in the presence of a catalyst system comprising a Ziegler-Natta (ZN-C) Catalyst, a cocatalyst (Co ) and, optionally, an external donor (ED), as described below.

[0098] The term sequential polymerization system according to this invention indicates that the heterophasic propylene copolymer is produced in at least two polymerization reactors connected in series. Consequently, the present polymerization system comprises at least a first polymerization reactor (R1), a second polymerization reactor (R2), optionally a third polymerization reactor (R3) and, optionally, still a fourth polymerization reactor (R4) ). The term polymerization reactor should indicate that the main polymerization occurs. Preferably, at least one of the two polymerization reactors (R1) and (R2) is a gas phase reactor (GPR). More preferably, the second polymerization reactor (R2), the third optional polymerization reactor (R3) and the fourth optional polymerization reactor (R4) are gas phase reactors (GPRs), that is, a first gas phase reactor ( GPR1) and a second gas phase reactor (GPR2) and a third gas phase reactor (GPR3). A gas phase reactor (GPR) according to this invention is preferably a fluidized bed reactor, a fluidized bed reactor

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25/69 fast or a sedimented bed reactor or any combination thereof.

[0099] Consequently, the first polymerization reactor (Rl) is preferably a slurry reactor (SR) and can be any simple or continuous agitated batch tank reactor or cycle reactor that operates in bulk or slurry . Bulk means polymerization in a reaction medium that comprises at least 60% (w / w) monomer. In accordance with the present invention, the

folder fluid ( SR) is, preferably a reactor of cycle (LR) ( in large scale) • [0100] In that first polymerization reactor (Rl), The homo- or copolymer of matrix propylene or part of same, this is, a first fraction of homo- and copolymer in

propylene, is produced.

[0101] Preferably, this propylene homo- or copolymer of the first polymerization reactor (R1), more preferably, the polymer slurry of the cycle reactor (LR) containing the matrix (M) or part thereof, i.e. ie, a first fraction of propylene homo- or copolymer, is directly fed into the second polymerization reactor (R2), that is, in the (first) gas phase reactor (GPR1), without an instant vaporization step between the stages.

[0102] This type of direct feed is described in documents EP 887379 A, EP 887380 A, EP 887381 A and EP 991684 A.

[0103] Direct feed means a process in which the content of the first polymerization reactor (Rl), that is, the cycle reactor (LR), the polymer slurry comprising the propylene homo- or copolymer matrix or

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26/69 part of it, that is, a first fraction of propylene homo- and copolymer, is taken directly to the next stage gas phase reactor.

[0104] Alternatively, the propylene homo- or copolymer of the first polymerization reactor (R1), preferably polymer slurry from the cycle reactor (LR) containing the propylene homo- or copolymer matrix or part of the same, it can also be directed to an instant vaporization stage or through an additional concentration stage before feeding into the second polymerization reactor (R2), that is, in the I ^the gas phase reactor (GPR1). Consequently, this indirect feeding refers to a process in which the content of the first polymerization reactor (Rl), the cycle reactor (LR), that is, the polymer slurry, is fed into the second polymerization reactor (R2) , in the (first) gas phase reactor (GPR1), by means of a reaction medium separation unit the reaction medium as a gas of the separation unit.

[0105] More specifically, the second polymerization reactor (R2) and any subsequent reactor, for example, the third (R3) or fourth polymerization reactor (R4) are preferably gas phase reactors (GPRs). Such gas phase reactors (GPR) can be any fluidized or mechanically mixed reactors. Preferably, the gas phase reactors (GPRs) comprise a mechanically agitated fluidized bed reactor with gas velocities of at least 0.2 m / sec. Thus, it is observed that the gas phase reactor is a fluidized bed type reactor, preferably with a

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27/69 mechanical stirrer.

[0106] Thus, in a preferred embodiment, the first polymerization reactor (Rl) is the slurry reactor (SR), as the cycle reactor (LR), while the second polymerization reactor (R2) and the third reactor optional polymerization reactor (R3), and the fourth optional polymerization reactor (R4) are gas phase reactors (GPRs).

[0107] Consequently, for the present process, at least two, preferably two, polymerization reactors (Rl), and (R2) or three polymerization reactors (Rl), (R2) and (R3), or even four reactors polymerization (Rl), (R2), R (3) and (R4), namely a slurry reactor (SR), as a cycle reactor (LR) and a (first) gas phase reactor (GPR1) , a second optional gas phase reactor (GPR2) and, optionally, a third gas phase reactor (GPR3) connected in series are used.

[0108] Before the slurry reactor (SR), a prepolymerization reactor is positioned.

[0109] As the process also covers a prepolymerization step, the entire Ziegler-Natta catalyst (ZN-C) is fed into the prepolymerization reactor. Subsequently, the prepolymerization product containing the Ziegler-Natta catalyst (ZN-C) is transferred to the first polymerization reactor (R1).

[0110] Especially good results are achieved if the temperature in the reactors is carefully chosen.

[0111] Consequently, it is preferred that the operating temperature in the first polymerization reactor

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28/69 (Rl) is in the range of 62 to 85 ° C, more preferably, in the range of 65 to 82 ° C, even more preferably, in the range of 67 to 80 ° C.

[0112] Alternatively or in addition to the previous paragraph, it is preferable that the operating temperature in the second polymerization reactor (R2) and the optional third reactor (R3) and the optional fourth reactor (R4) is in the range of 75 to 95 ° C, more preferably, in the range of 78 to 92 ° C.

[0113] Preferably, the operating temperature in the second polymerization reactor (R2) is equal to or greater than the operating temperature in the first polymerization reactor (Rl). Consequently, it is preferred that the operating temperature

(The) in the first polymerization reactor (Rl) is in the range 62 to 85 ° C, more preferably, in the range of 65 at 82 ° C, even more preferably, in the range of 67 to

° C, such as 70 to 80 ° C;

and

(B) in the second polymerization reactor (R2) is in the range 75 to 95 ° C, more preferably in the range of 78 at 92 ° C, 88 ° C, even more preferably, in the range of 78 to with the condition that the operating temperature in the

second polymerization reactor (R2) is equal to or greater than the operating temperature in the first polymerization reactor (Rl).

[0114] Typically, the pressure in the first

polymerization (Rl), preferably in the cycle reactor (LR), is in the range of 2 to 8 MPa (20 to 80 bar), from

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29/69 preferably, 3 to 7 MPa (30 to 70 bar), as 3.5 to 6.5 MPa (35 to 65 bar), while the pressure in the second polymerization reactor (R2), that is, in the (first ) gas phase reactor (GPR1), and in any subsequent reactor, such as in the third polymerization reactor (R3), for example, in the second gas phase reactor (GPR2), or in a fourth polymerization reactor (R4), for example For example, in the third gas phase reactor (GPR3) it is in the range of 0.5 to 5 MPa (5 to 50 bar), preferably 1.5 to 4 MPa (15 to 40 bar).

[0115] Preferably, hydrogen is added to each polymerization reactor in order to control the molecular weight, ie the MFR2 melt flow rate.

[0116] Preferably, the average residence time is longer in the polymerization reactors (R1) and (R2). In general, the average residence time (T) is defined as the ratio between the reaction volume (VR) and the reactor volumetric efflux rate (Qo) (ie, VR / Qo), that is, T = VR / Qo [tau = VR / Qo]. In this case of a cycle reactor, the reaction volume (VR) is equal to the reactor volume.

[0117] Consequently, the average residence time (t) in the first polymerization reactor (Rl) is preferably at least 5 min, more preferably, in the range of 15 to 80 min, even more preferably, in the range of 20 at 60 min, as in the 24 to 50 min range, and / or the average residence time (T) in the second polymerization reactor (R2) is preferably at least 70 min,

more preferably, at banner of 7 0 The 220 min, still more preferably, at banner of 8 0 The 210 min, still more preferably, at banner from 90 to 200 min, as in banner from 90 to 190 min. Preferably would, the time of

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30/69 average permanence (T) in the third polymerization reactor (R3) or in the fourth polymerization reactor (R4) - if present- it is preferably at least 30 min, more preferably, in the range of 30 to 120 min, even more preferably, in the 40 to 100 min range, as in the 50 to 90 min range.

[0118] As mentioned above, the preparation of the heterophasic propylene copolymer preferably comprises, in addition to the (main) polymerization of the propylene polymer in the at least two polymerization reactors (R1, R2 and R3, R4 optional) before it, a prepolymerization in an upstream prepolymerization (PR) reactor for the first polymerization reactor (Rl).

[0119] In the prepolymerization (PR) reactor, a polypropylene (Pre-PP) is produced. Prepolymerization is carried out in the presence of the Ziegler-Natta catalyst (ZN-C). According to this modality, the Ziegler-Natta catalyst

(ZN-C), the cocatalyst (Co), and the external donor (ED) are all introduced in step of prepolymerization. At the however , this should not delete the option that in a internship later by example, cocatalyst (Co) and / or donor external (ED) additional are added at the

polymerization process, for example, in the first reactor (Rl). In one embodiment, the Ziegler-Natta catalyst (ZNC), the cocatalyst (Co), and the external donor (ED) are only added to the prepolymerization (PR) reactor.

[0120] The prepolymerization reaction is typically conducted at a temperature of 10 to 60 ° C, preferably 15 to 50 ° C and, more preferably, 20 to 45 ° C.

[0121] The pressure in the prepolymerization reactor is not

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31/69 criticizes, but it must be high enough to keep the reaction mixture in liquid phase. Thus, the pressure can be from 2 to 10 MPa (20 to 100 bar), for example, 3 to 7 MPa (30 to 70 bar).

[0122] In a preferred embodiment, prepolymerization is conducted as bulk polymerization in liquid propylene, that is, the liquid phase comprises mainly propylene, with optionally inert components dissolved in it. In addition, according to the present invention, an ethylene feed can be employed during prepolymerization as mentioned above.

[0123] It is possible to add other components to the prepolymerization stage as well. In this way, hydrogen can be added in the prepolymerization stage to control the molecular weight of polypropylene (Pre-PP), as is known in the art. In addition, antistatic additive can be used to prevent particles from adhering to each other or to the reactor walls.

[0124] Precise control of prepolymerization conditions and reaction parameters is inherent to technical aptitude.

[0125] Due to the process conditions defined above in the prepolymerization, a mixture of the ZieglerNatta catalyst (ZN-C) and the polypropylene (Pre-PP) produced in the prepolymerization (PR) reactor is obtained. Preferably, the Ziegler-Natta (ZN-C) catalyst is (finely) dispersed in the polypropylene (Pre-PP). In other words, the Ziegler-Natta (ZN-C) catalyst particles introduced in the prepolymerization (PR) reactor are divided into

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32/69 smaller fragments that are equally distributed within the growing polypropylene (Pre-PP). The sizes of the introduced Ziegler-Natta catalyst particles (ZNC), as well as the fragments obtained are not of essential relevance to the present invention and are within qualified knowledge.

[0126] Consequently, the heterophasic propylene copolymer is preferably produced in a process that comprises polymerization of propylene in at least two subsequent polymerization steps in the presence of a Ziegler-Natta catalyst, in which:

a) in the first polymerization reactor (Rl), that is, in a cycle reactor (LR), propylene is optionally polymerized in the presence of a comonomer, obtaining either a first fraction of propylene homo- and copolymer or the homo matrix - or propylene copolymer (M), which transfers said first fraction of propylene homo- and copolymer or the propylene homo- or copolymer matrix (M) to a second polymerization reactor (R2),

b) in the second polymerization reactor (R2) or in a second fraction of propylene homo- and copolymer, together with the first fraction of propylene homo- and copolymer, form the propylene homo- or copolymer matrix (M), or fraction of predominantly amorphous ethylene copolymer (a2) in the presence of the propylene (M) homo- or copolymer matrix produced in the previous step a) is produced, in which

c) if in the first and second polymerization reactor the matrix of propylene homo- or copolymer (M) is produced, in a third polymerization reactor (R3), the

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33/69 fraction of predominantly amorphous ethylene copolymer (a2) in the presence of the propylene homo- or copolymer matrix (M) produced in the previous steps a) and b) is produced.

[0127] In another preferred process, a prepolymerization step is also included before the reaction in the first polymerization reactor (Rl).

[0128] In such a prepolymerization step, before the reaction in the first polymerization reactor (Rl), a mixture of the Ziegler-Natta catalyst (ZN-C) and the polypropylene (Pre-PP) produced in the prepolymerization reactor (PR ) is obtained. Preferably, the catalyst

Ziegler-Natta (ZN-C) is (finely) dispersed in polypropylene (Pre-PP). Subsequent to prepolymerization, the mixture of the Ziegler-Natta catalyst (ZN-C) and the polypropylene (Pre-PP) produced in the prepolymerization reactor (PR) is transferred to the first reactor (Rl). Typically, the total amount of polypropylene (Pre-PP) in the final heterophasic propylene copolymer (RAHECO) is, instead, low and typically no more than 5.0% by weight, more preferably, no more than 4.0% in weight, even more preferably, in the range of 0.5 to 4.0% by weight, as in the range of 1.0 to 3.0% by weight.

[0129] A preferred multistage process is a gas phase cycle process, as developed by Borealis (known as BORSTAR® technology) and is described, for example, in patent literature, as in EP 0 887 379, WO 92/12182 WO 2004/000899, WO

2004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.

[0130] An additional gaseous-slurry process

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is the process Basell Spheripol®. [0131] The components of catalyst are of preferably, all introduced at stage of pre-

polymerization. However, when the solid catalyst component (i) and the cocatalyst (ii) can be fed separately, it is possible that only a part of the cocatalyst is introduced in the prepolymerization stage and the remainder in subsequent polymerization stages. In addition, in such cases, it is necessary to introduce a lot of cocatalyst in the prepolymerization stage so that a sufficient polymerization reaction is obtained in it.

[0132] It is possible to add other components also to the prepolymerization stage. In this way, hydrogen can be added to the prepolymerization stage to control the molecular weight of the prepolymer, as is known in the art. In addition, antistatic additive can be used to prevent particles from adhering to each other or to the reactor walls.

[0133] Precise control of prepolymerization conditions and reaction parameters is within the skill of the technique.

[0134] According to the invention, the heterophasic polypropylene composition is obtained by a multi-stage polymerization process, as described above, in the presence of a catalyst system.

[0135] In the process described above, a Ziegler-Natta (ZN-C) catalyst for the preparation of the heterophasic polypropylene composition is applied. This Ziegler-Natta (ZN-C) catalyst can be any Ziegler catalyst

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Stereo-specific Natta (ZN-C) for propylene polymerization, which preferably has the ability to catalyze the polymerization and copolymerization of propylene and comonomers at a pressure of 500 to 10,000 kPa, in particular 2,500 to 8,000 kPa, and at a temperature from 40 to 110 ° C, in particular from 60 to 110 ° C.

[0136] Preferably, the Ziegler-Natta (ZNC) catalyst comprises a high performance Ziegler-Natta type catalyst including an internal donor component, which can be used at high polymerization temperatures of 80 ° C or more.

[0137] Such a high performance Ziegler-Natta catalyst (ZN-C) can comprise a succinate, a diether, a phthalate etc., or mixtures thereof as an internal donor (ID) and are, for example, commercially available, for example , with LyondellBasell under the trade name Avant ZN.

[0138] Especially useful solid catalysts are also those disclosed in WO-A2003 / 000757, WO-A-2003/000754, WO-A-2004/029112 and W02007 / 137853. These catalysts are solid spherical catalysts with compact structure and little surface area of the particles. In addition, these catalysts are portrayed by a uniform distribution of catalytically active sites across the catalyst particles. The catalysts are prepared by the emulsion-solidification method, in which no external support is required. The dispersed phase in the form of liquid droplets of the emulsion forms the catalyst part, which is transformed into solid catalyst particles during the solidification step. Thus, in a modality

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36/69 of the present invention, the solid catalyst component is prepared by a process comprising:

- prepare a magnesium complex solution by reacting an alkoxy magnesium compound and an electron donor or a precursor thereof in a C6-C10 aromatic liquid reaction medium;

- reacting the magnesium complex site with a quadrivalent titanium compound, preferably TiCI4, at a temperature greater than 10 ° C and less than 50 ° C to produce a dispersed, more dense phase emulsion that is right in mol of Ti / Mg from 0.1 to 10 and in a continuous phase that has a mol ratio of Ti / Mg from 10 to 100; and stirring the emulsion, optionally in the presence of an emulsion stabilizer and / or a turbulence-minimizing agent, in order to keep the droplets of said dispersed phase within an average size range of 5 to 200 pm.

[0139] The catalyst particles are obtained after solidification of said droplets of the dispersed phase by heating, preferably at a temperature of 80 ° C to 110 ° C. In said process, an alkyl aluminum compound of the formula AIR3-nXn, wherein R is an alkyl and / or alkoxy group of 1 to 20, preferably 1 to 10 carbon atoms, X is a halogen and n is 0, 1 or 2, is added and placed in contact with the droplets of the dispersed phase of the stirred emulsion. Alternatively, the alkyl aluminum compound of the formula AIR3-nXn, is placed in contact with the solidified particles in the washing step before recovering the final solid particles.

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[0140] Suitable internal electron donors are, among others, (di) esters of aromatic (di) carboxylic acids. Said aromatic carboxylic acid ester or diester can be formed, on site, by reaction of an aromatic carboxylic acid chloride or diacid chloride with a C2C16 alkanol and / or diol, and is preferred di-2-ethylhexyl phthalate.

[0141] An additional suitable catalyst for the present invention is a solid Ziegler-Natta catalyst, comprising IUPAC Group 4 to 6 transition metal compounds, such as titanium, a Group 2 metal compound, such as magnesium, and an internal donor which is a non-phthalic compound, more preferably, a non-phthalic acid ester, even more preferably, which is a diester of non-phthalic dicarboxylic acids, as described in greater detail below. In this way, the catalyst is completely free of unwanted phthalic compounds. In addition, the solid catalyst is free of any external support material, such as silica or MgCl2, but the catalyst is self-supporting.

[0142] The Ziegler-Natta (ZN-C) catalyst can be further defined by the way it is obtained.

[0143] Consequently, the Ziegler-Natta (ZN-C) catalyst is preferably obtained by a process comprising the steps of

a) ai) to provide a solution of at least one Group 2 metal alkoxy compound (Ax) which is the reaction product of a Group 2 metal compound and a monohydric alcohol (A) comprising, in addition to the chemical portion of

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38/69 hydroxyl, at least a chemical portion of ether, optionally, in an organic liquid reaction medium; or a2) a solution of at least one Group 2 metal alkoxy compound (Ax ') which is the reaction product of a Group 2 metal compound and a mixture of monohydric alcohol (A) and an alcohol monohydric (B) of formula ROH, optionally, in an organic liquid reaction medium; or as) provide a solution of a mixture of the Group 2 alkoxy compound (Ax) and a Group 2 metal alkoxy compound (Bx) which is the reaction product of a Group 2 metal compound and the mono- water (B), optionally, in an organic liquid reaction medium; or a4) provide a solution of Group 2 alkoxide of formula M (ORi) n (OR2) mX2-nm or mixture of Group 2 alkoxides M (ORi) n'X2-n 'and M (OR2) m'X2- m ', where M is Group 2 metal, X is halogen, Ri and R2 are different alkyl groups from C2 to C1 carbon atoms, and 0 <n <2, 0 <m <2 and n + m-ι- (2-nm) = 2, provided that both n and my 0, 0 <n '<2 and 0 <m' <2; and

b) adding said solution from step a) to at least one compound of a transition metal of Group 4 to 6 and

c) obtain the solid catalyst component particles, and add an internal non-phthalic donor, in any step prior to step c).

[0144] The internal donor or precursor of the same is preferably added to the solution in step a).

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[0145] According to the procedure above, the Ziegler-Natta catalyst can be obtained by means of precipitation method or by emulsion (liquid / liquid two-phase system) - solidification method depending on physical conditions, especially temperature used in steps b) and c).

[0146] In both methods (precipitation or emulsion solidification), the catalyst chemistry is the same.

[0147] In combination of the precipitation method of the solution from step a) with at least one transition metal compound in step b) is carried out and the entire reaction mixture is kept at least at 50 ° C, more preferably, in the range temperature from 55 ° C to 110 ° C, more preferably in the range of 70 ° C to 100 ° C, to maintain complete precipitation of the component catalyst in the form of solid particles (step c).

[0148] In the solidification-emulsion method in step b), the solution from step a) is typically added to at least one transition metal compound at a lower temperature, such as from -10 to below 50 ° C, preferably , from -5 to 30 ° C. During the stirring of the emulsion, the temperature is typically maintained at -10 to below 40 ° C, preferably from -5 to 30 ° C. The droplets of the dispersed phase of the emulsion form the active catalyst composition. The solidification (step c) of the droplets is suitably carried out by heating the emulsion to a temperature of 70 to 150 ° C, preferably to 80 to 110 ° C.

[0149] The catalyst prepared by the solidification-emulsion method is preferably used in the present invention.

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[0150] In a preferred embodiment in step a) the solution of a2) or as) is used, that is, a solution of (Ax ') or a solution of a mixture of (Ax) and (Bx).

[0151] Preferably, the Group 2 metal is magnesium.

[0152] The magnesium alkoxy compounds (Ax), (Ax ') and (Bx) can be prepared on site in the first step of the catalyst preparation process, step a), by reacting the magnesium compound with alcohol ( or alcohols), as described above, or said magnesium alkoxy compounds may be separately prepared magnesium alkoxy compounds or they may still be commercially available as magnesium alkoxy compounds ready and used in this way in the catalyst preparation process. of the invention.

[0153] Illustrative examples of alcohols (A) are monoethers of dihydric alcohols (glycol monoethers). Preferred alcohols (A) are C2 to C4 glycol monoethers, wherein the ether fractions comprise from 2 to 18 carbon atoms, preferably from 4 to 12 carbon atoms. Preferred examples are 2- (2-ethylhexyloxy) ethanol, 2butyloxy ethanol, 2-hexyloxy ethanol and 1,3-propylene glycol-monobutyl ether, 3-butoxy-2-propanol, with 2- (2-ethylhexyloxy) ethanol and ether 1,3-propylene-glycol-monobutyl, where 3-butoxy-2-propanol is particularly preferred.

[0154] The illustrative monohydric alcohols (B) are of the formula ROH, where R is residue of Ce-C10 straight or branched chain alkyl. The most preferred monohydric alcohol is 2-ethyl-1-hexanol or octanol.

[0155] Preferably, a mixture of Mg alkoxide compounds (Ax) and (Bx) or mixture of alcohols (A) and (B),

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41/69 respectively, are used and employed in a mol ratio of Bx: Ax or B: A from 8: 1 to 2: 1, more preferably, 5: 1 to 3: 1.

[0156] Magnesium alkoxy compound can be an alcohol reaction product (alcohols) as defined above, and a magnesium compound selected from dialkyl magnesium, alkyl magnesium alkoxides, magnesium dialcoxides, magnesium alkoxide halides alkyl magnesium. Alkyl groups can be a similar or different C1-C20 alkyl, preferably C2-C10 alkyl. Typical alkyl-alkoxy magnesium compounds, when used, are ethyl magnesium butoxide, butyl magnesium pentoxide, octyl magnesium butoxide and octyl magnesium octoxide. Preferably, dialkyl magnesium is used. Most preferred dialkyl magnesium is butyl octyl magnesium or butyl ethyl magnesium.

[0157] It is also possible that the magnesium compound can react, in addition to alcohol (A) and alcohol (B), also with a polyhydric alcohol (C) of formula R (0H) _m to obtain said compounds of magnesium alkoxide. Preferred polyhydric alcohols, if used, are alcohols, where R is a C2 to CIO linear, cyclic or branched chain hydrocarbon residue, and is an integer 2 to 6.

[0158] The magnesium alkoxy compounds of step a) are therefore selected from the group consisting of magnesium dialcoxides, magnesium diaryloxides, magnesium alkoxide halides, magnesium aryloxide halides, alkyl magnesium alkoxides, aryl magnesium alkoxides and alkyl magnesium aryloxides. In addition, a

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42/69 mixture of magnesium dihalide and a magnesium dialoxide can be used.

[0159] The solvents to be used for the preparation of the present catalyst can be selected from straight, branched and cyclic aromatic and aliphatic hydrocarbon chains with 5 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, or mixtures of the themselves. Suitable solvents include benzene, tiluene, cumene, xylol, pentane, hexane, heptane, octane and nonane. Hexanes and pentanes are particularly preferred.

[0160] The Mg compound is typically supplied as a 10 to 50% by weight solution in a solvent, as indicated above. The typical commercially available Mg compound, especially dialkyl magnesium solutions are solutions of 20 to 40% by weight in tiluene or heptanes.

[0161] The reaction for the preparation of the magnesium alkoxy compound can be carried out at a temperature of 40 ° to 70 ° C. The most suitable temperature is selected depending on the Mg and alcohol compound (or alcohols) used.

[0162] The transition metal compound from Group 4 to 6 is preferably a titanium compound, most preferably a titanium halide, such as TICI4.

[0163] The internal non-phthalic donor used in the preparation of the catalyst used in the present invention is preferably selected from non-phthalic (di) carboxylic (di) esters, 1,3-diethers, derivatives and mixtures thereof . Especially preferred donors are diesters of monounsaturated dicarboxylic acids, in particular esters that belong to a group comprising malonates, maleates, succinates,

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43/69 citraconates, glutarates, cyclohexene-1,2-dicarboxylates and benzoates, and any derivatives and / or mixtures thereof. Preferred examples are, for example, substituted maleates and citraconates, most preferably citraconates.

[0164] In the emulsion method, the two-phase liquid-liquid system can be formed by simple stirring and, optionally, add (still) solvent (or solvents) and additives, such as the turbulence minimizing agent (TMA) and / or emulsifying agents and / or emulsion stabilizers, such as surfactants, which are used in a manner known in the art to facilitate the formation of and / or stabilize the emulsion. Preferably, surfactants are acrylic or methacrylic polymers. Particularly preferred are C12 to C20 unbranched (meth) acrylates such as poly (hexadecyl) -methacrylate and poly (octadecyl) methacrylate and mixtures thereof. Turbulence-minimizing agent (TMA), if used, is preferably selected from α-olefin polymers of aolefin monomers with 6 to 20 carbon atoms, such as polyoctene, polynonene, polydecene, polyundecene or polydodecene or mixtures of the same. Most preferred is polydecene.

[0165] The solid particulate product obtained by precipitation or solidification-emulsion method can be washed at least once, preferably at least twice, most preferably, at least three times with an aromatic and / or aliphatic hydrocarbon, preferably with toluene, heptane or pentane. The catalyst can also be dried, such as by evaporation or washing with nitrogen, or it can be a slurry for an oily liquid without

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44/69 any drying step.

[0166] The finally obtained Ziegler-Natta catalyst is desirable in the form of particles which, in general, have an average particle size range of 5 to 200 pm, preferably 10 to 100. The particles are compact with low porosity and have a surface area below 20 g / m ² , more preferably below 10 g / m ² . Typically, the amount of Ti is 1 to 6% by weight, Mg from 10 to 20% by weight and donor from 10 to 40% by weight of the catalyst composition.

[0167] The detailed description of the preparation of catalysts is disclosed in WO 2012/007430, EP2610271, EP 261027 and EP2610272, which are incorporated by reference for this document.

[0168] The Ziegler-Natta (ZN-C) catalyst is preferably used in association with an alkyl aluminum (Co) cocatalyst and, optionally, external donors (ED).

[0169] As an additional component in the present polymerization process, an external donor (ED) is preferably present. Suitable external donors include certain silanes, ethers, esters, amines, ketones, heterocyclic compounds and mixtures thereof. It is especially preferable to use a silane. It is more preferable to use silanes of the general formula

RapRbqSi (ORc) (4-pq) where Ra, Rb and Rc represents, a hydrocarbon radical, in particular, an alkyl or cycloalkyl group, and where p and q are numbers that are in the range 0 to 3, where their sum p + q is equal to or less than 3. Ra,

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Rb and Rc can be chosen independently of each other and can be the same or different. Specific examples of such silanes are (tert-butyl) 2Si (OCH3) 2, (cyclohexyl) (methyl) Si (OCH3) 2, (phenyl) 2Si (OCH3) 2 and (cyclopentyl) 2Si (OCH3) 2, or of formula general

Si (OCH2CH3) 3 (NR ³ R ⁴ ) where R ³ and R ⁴ can be the same or different from a representation of a hydrocarbon group having 1 to 12 carbon atoms.

[0170] R ³ and R ⁴ are independently selected from the group consisting of linear aliphatic hydrocarbon group having 1 to 12 carbon atoms, branched aliphatic hydrocarbon group having 1 to 12 carbon atoms and cyclic aliphatic hydrocarbon group having 1 to 12 carbon atoms. In particular, it is preferable that R ³ and R ⁴ are independently selected from the group consisting of methyl, ethyl, n-propyl, nbutyl, octyl, decanyl, iso-propyl, iso-butyl, isopentyl, tert-butyl, tert-amyl, neopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl and cycloheptyla.

[0171] More preferably, both R ³ and R ⁴ are equal, even more preferably, both R ³ and R ⁴ are an ethyl group.

[0172] External donors (ED) that are particularly preferred are the dicyclopentyl dimethoxy silane donor (D-donor) or the cycloheximethyl dimethoxy silane donor (C-Donor).

[0173] In addition to the Ziegler-Natta catalyst (ZN-C) and the optional external donor (ED), a cocatalyst (Co) can

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46/69 be used. The cocatalyst (Co) is preferably a compound of group 13 of the periodic table (IUPAC), for example, organo aluminum, as an aluminum compound, such as alkyl aluminum, aluminum halide or alkyl aluminum halide compound. Consequently, in a specific modality, the cocatalyst (Co) is a trialkylaluminium, such as triethylaluminium (TEAL), dialkyl aluminum chloride or alkyl aluminum dichloride or mixtures thereof. In a specific modality, the cocatalyst (Co) is triethyl aluminum (TEAL).

[0174] Preferably, the ratio between the cocatalyst (Co) and the external donor (ED) [Co / ED] and / or the ratio between the cocatalyst (Co) and the transition metal (TM) [Co / TM] must be carefully chosen.

[0175] Consequently, (a) the molar ratio between cocatalyst (Co) and donor

external (ED) [Co / ED] should to be in banner in 5 to 45, from preferably, is in range 5 The 35, more preferably, it is in the range in 5 at 25; and, optionally, (b) the molar ratio between cocatalyst (Co) it's composed titanium (TC) [Co / TC] must be on the banner in above 80

500 to preferably be in the range of 100 to 350, even more preferably to be in the range of 120 to 300.

[0176] The heterophasic polypropylene composition according to that invention is preferably produced in the presence of (a) a Ziegler-Natta (ZN-C) catalyst comprising an internal donor (TD), (b) optionally, a cocatalyst (Co), and

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47/69 (c) optionally, an external donor (ED).

[0177] As mentioned above, the ZieglerNatta (ZN-C) catalyst is optionally modified by the so-called BNT technology during the prepolymerization step described above in order to introduce the polymeric nucleating agent.

[0178] Such a polymeric nucleating agent is, as described above, a vinyl polymer, such as a vinyl polymer derived from monomers of the formula CH2 = CH-CHR1R2, as described above.

[0179] The weight ratio between vinyl compound and polymerization catalyst in the polymerization catalyst modification step is preferably 0.3 or more to 40, such as 0.4 to 20 or, more preferably, 0.5 to 15, such as 0.5 to 2.0.

[0180] The polymerization of the vinyl compound, for example VCH, can be carried out in any inert fluid that does not dissolve the polymer formed (for example, polyVCH). It is important to ensure that the viscosity of the final polymerized composite / inert fluid / vinyl mixture is high enough to prevent the catalyst particles from settling during storage and transportation.

[0181] The adjustment of the viscosity of the mixture can be carried out either before or after the polymerization of the vinyl compound. It is, for example, possible to carry out the polymerization in a low viscosity oil and, after the polymerization of the vinyl compound, the viscosity can be adjusted by adding a highly viscous substance. Such a highly viscous substance can be a wax, like an oil or a

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48/69 mixing an oil with a highly viscous or solid substance (oil-grease). The viscosity of such a viscous substance is, in general, 1,000 to 15,000 cP at room temperature. The advantage of using wax is that the storage and feeding of catalyst in the process is improved. Since no washing, drying, screening and transfer are necessary, the catalyst activity is maintained.

[0182] The weight ratio between the oil and the highly viscous or solid polymer is preferably less than 5: 1.

[0183] In addition to the viscous substances, liquid hydrocarbons, such as isobutane, propane, pentane and hexane, can also be used as a medium in the modification step.

[0184] Polypropylenes produced with a catalyst modified with polymerised vinyl compounds do not essentially contain free (unreacted) vinyl compounds. This means that vinyl compounds must be completely reacted in the catalyst modification step. For this purpose, the weight ratio between the (added) vinyl compound and the catalyst should be in the range of 0.05 to 10, preferably less than 3, more preferably, about 0.1 to 2.0 and , in particular, about 0.1 to 1.5. It should be noted that no benefit is achieved by using excess vinyl compounds.

[0185] Furthermore, the reaction time of the catalyst modification by polymerization of a vinyl compound must be sufficient to allow complete reaction of the vinyl monomer, that is, the polymerization is continued until the amount of unreacted vinyl compounds in the reaction mixture (including polymerization medium and reagents)

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49/69 is less than 0.5% by weight, in particular, less than 2,000 ppm by weight (shown by analysis). Thus, when the prepolymerized catalyst contains a maximum of about 0.1% by weight of vinyl compound, the final content of vinyl compound in the polypropylene will be below the limit of determination using the GC-MS method ( <0.01 ppm by weight). In general, when operating on an industrial scale, a polymerization time of at least 30 minutes is required, preferably the polymerization time is at least 1 hour and, in particular, at least 5 hours. Polymerization times even in the range of 6 to 50 hours can be used. The modification can be carried out at temperatures of 10 to 60 ° C, preferably 15 to 55 ° C.

[0186] The general conditions for the modification of the catalyst are also disclosed in WO 00/6831, incorporated in this document by way of reference in relation to the modification of the polymerization catalyst. Preferred embodiments, as described earlier in the present application, with respect to the vinyl compound also apply with respect to the polymerization catalyst of the present invention and the preferred polypropylene composition according to the present invention.

[0187] Suitable means for the modification step include, in addition to oils, also inert organic solvents with low viscosity, such as pentane and heptane. In addition, small amounts of hydrogen can be used during modification.

Component (B) styrene-based elastomer

[0188] The additional required component in this

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50/69 invention is a styrene-based elastomer.

[0189] It has been found that not any styrene-based elastomer is suitable for the present invention, but only a specific class of such elastomers. Accordingly, for the present invention, a styrene-based elastomer is an unsaturated styrene block copolymer that contains at least one diene comonomer, preferably selected from butadiene and isoprene and which has a styrene content of 5, 0 to 50.0% by weight measured by Fourier transform infrared spectroscopy (FTIR).

[0190] Consequently, it is observed that the styrene-based elastomer (B), preferably a styrene-isoprene-styrene block copolymer (SIS), a styrene-butadiene-styrene block copolymer (SBS) or a styrene-isoprene-butadiene-styrene block copolymer (SIBS), more preferably a styrene-isoprene-styrene block copolymer (SIS), has a styrene content of at least 5.0% by weight, preferably at least 10.0% by weight and, more preferably, at least 15.0% by weight. The upper limit is 50.0% by weight, preferably 40.0% by weight, more preferably 35.0% by weight and, even more preferably, 30.0% by weight.

[0191] Furthermore, it is observed that the styrene-based elastomer (B), preferably a styrene-isoprene-styrene block copolymer (SIS) has a melting flow rate MFR2 (230 ° C, ISO 1133) of not more than 200.0 g / 10 min, preferably not more than 150.0 g / 10 min and, more preferably, not more than 100.0 g / 10 min.

[0192] On the other hand, the melt flow rate of the

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51/69 styrene-based elastomer (B), preferably a styrene-isoprene-styrene block copolymer (SIS) or a styrene-butadiene-styrene block copolymer, more preferably a styrene-block copolymer.

isoprene-styrene (SIS), no must fall below in 2.0 g / 10 min. Consequently, a preferred range is in 2.0 to 200.0 g / 10 min, more preferential, in θ, 0 The 150.0 g / 10min and, still more preferential, in 10, 0 The 100.0 g / 10 min. [0193] Furthermore, the elastomer styrene-based (B) in

Preferably, a styrene-isoprene styrene block copolymer (SIS) can be defined by its density.

[0194] Thus, it is observed that the styrene-based elastomer (B), preferably a styrene-isoprene-styrene block copolymer (SIS), has a density of 0.900 g / cm ³ to 0, 950 g / cm ³ , preferably from 0.910 g / cm ³ to 0.950 g / cm ³ and, more preferably, from 0.915 to 0.455 g / cm ³ .

[0195] Additionally or alternatively, the styrene-based elastomer (B), preferably a styrene-isoprene-styrene block copolymer (SIS) can be defined

by Shore hardness A. In this way, it is observed what The styrene-based elastomer (B) has a toughness Shore THE measure according with ASTM D 2240 from 2 5 to 80, in preferably from 30 to 75. [0196] Examples of elastomer at base styrene (B) are the product line - DEXCO TSRC VECTOR for SIS and SBS, marketed as VECTOR 4111A (SIS, Shore A hardness in

40, styrene content of 18% by weight, density

0.93 g / cm ³ ), VECTOR 4211 (SIS, 29% by weight styrene,

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density 0.94 g / cm ³ , Shore A 68 ) or VECTOR 8508 (SBS, 29% by weight styrene, density 0, 94 g / cm ³ , Shore A 67); or products available together The Kraton D (SBS), lines of

Kraton D (SIS) or Kraton S (SIBS) product, such as, for example, Kraton D1102 A (SBS, 29.5% by weight of styrene, density 0.94 g / cm ³ , Shore A 70), Kraton Dllll K (SIS, 22% by weight of styrene, density 0.93 g / cm ³ , Shore A 45) or Kraton

D1119 B i ! SIS, 16% in weight of styrene, density 0.94 g / cm ³ , Shore A 38 ) or gives line of product - Versalis Eni Europrene for SIS and SBS, Europrene SOL T 190 exemplary ( SIS, 16% in styrene weight, density 0.92 g / cm ³ , Shore A so: 1 or Europrene SOL T 6205 (SBS, 25%

by weight of styrene, density 0.93 g / cm ³ , Shore A 68).

Ad) composition of grafted heterophasic propylene copolymer

[0197] The composition of the present invention comprises component (A) and component (B) as described above, wherein component (B) is grafted onto component (A).

[0198] The amount of component (A), the base heterophasic propylene copolymer, is present in an amount of 30.0 to 95.0% by weight, preferably from 40.0 to 90.0% by weight , more preferably, from 50.0 to 85.0% by weight and, even more preferably, from 55.0 to 80.0% by weight.

[0199] Thus, the amount of component (B), the styrene-based elastomer, is present in an amount of 5.0 to 70.0% by weight, preferably from 10.0 to 60.0% by weight, more preferably, from 15.0 to 50.0% by weight and, even more preferably, from 20.0 to 45.0% by weight.

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[0200] The grafted heterophasic propylene copolymer composition is characterized by a composition melt flow rate (MFRc) (ISO 1133; 230 ° C; 2.16 kg) in the range of 0.5 to 50.0 g / 10 min, preferably in the range of 1.0 to 40.0 g / 10 min, more preferably, in the range of 1.5 to 30.0 g / 10 min and, even more preferably, in the range of 2.0 at 15.0 g / 10 min.

[0201] The composition of grafted heterophasic propylene copolymer is still and / or alternatively defined by the gel content. The gel content is a good indicator for the chemical modification of the inventive composition (indication of unwanted crosslinking).

[0202] It is preferable that the gel content is kept to a lower degree, which means that in the process of preparing the inventive composition, the predominant reaction is non-crosslinking graft. Consequently, the present invention is depicted by a gel content in the range of 0.05% by weight less than 5.00% by weight determined as the relative amount of boiling xylene insoluble polymer (insoluble hot xylene fraction, XHI). Preferably, the gel content of the inventive composition is in the range of 0.10% by weight to 2.00% by weight and, more preferably, in the range of 0.15% by weight to 1.50% by weight.

[0203] Furthermore, the grafted heterophasic propylene copolymer composition of the present invention preferably has a tension module measured according to ISO 527-1.2 (beam speed = 1 mm / min) below 350 MPa preferably below 320 MPa and, more preferably, below 300 MPa. The lower limit

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54/69 can be 100 MPa, preferably 200 MPa.

[0204] In addition, it is preferred that the grafted heterophasic propylene copolymer composition of the present invention has a higher impact strength, especially at low temperatures. Consequently, the inventive composition has an impact resistance measured according to the Charpy cut impact test according to ISO 17 9 (leA) at 20 ° C of at least 15.0 kJ / m ² , preferably at least at least 30.0 kJ / m ² , more preferably at least 50.0 kJ / m ² and, even more preferably, at least 65 kJ / m ² .

[0205] 0 upper limit of impact test per cut

Charpy in a deal with ISO 179 (leA) a -20 ° C can be 150 kJ / m ² , in preferably, 100 kJ / m ² . [0206] Besides that, The composition inventive has a

impact strength measured according to the Charpy cut impact test according to ISO 17 9 (leA) at 30 ° C of at least 7.0 kJ / m ² , preferably at least 10.0 kJ / m ² , more preferably, at least 12.0 kJ / m ² and, even more preferably, at least 14 kJ / m ² .

[0207] 0 upper limit of impact test per cut

Charpy according to ISO 179 (leA) at -30 ° C can be 60 kJ / m ² , preferably 50 kJ / m ² .

[0208] The grafted heterophasic propylene copolymer composition of the present invention has an F30 fusion resistance of at least 3.0 cN, preferably at least 4.5 cN and, more preferably, at least 5.0 cN , where the resistance

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55/69 F30 fusion is measured with the Rheotens test at 200 ° C according to ISO 16790: 2005.

Preparation of grafted heterophasic propylene copolymer composition

[0209] The grafted heterophasic propylene copolymer composition of the present invention can be prepared by a simple grafting process, which can also be called a reactive fusion modification process.

[0210] The selection of these two specific polymers (A) and (B) guarantees good compatibility of the two components, taking into account an efficient and homogeneous polymer graft (B) in the polymer (A).

[0211] Thus, according to an additional embodiment, the present invention relates to a process for producing the grafted heterophasic propylene copolymer composition, in which such a process is a reactive fusion modification process comprising the steps of

i) mixing component (A), the heterophasic polypropylene copolymer with component (B), the styrene-based elastomer and a thermal decomposition free radical forming compound (C) and ii) extruding said mixture.

[0212] In this process, a thermal decomposition free radical forming compound (C) is added to initiate the styrene-based elastomer graft reaction (B) in the base heterophasic propylene copolymer (A).

[0213] Peroxides are radical forming agents

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56/69 free of thermal decomposition preferred.

[0214] The peroxides listed below are, in particular, preferred:

Acyl peroxides: benzoyl peroxide, 4-chlorobenzoyl peroxide, 3-methoxybenzoyl peroxide and / or methyl benzoyl peroxide.

Alkyl peroxides: allyl-t-butyl peroxide, 2,2-bis (t-butylperoxybutane), 1,1-bis (t-butylperoxy) - 3,3,5-trimethylcyclohexane valerate, n-butyl-4 , 4-bis (tbutilperoxy), diisopropylaminomethyl-t-amyl peroxide, dimethylaminomethyl-tamyl peroxide, diethylaminomethyl-t-butyl peroxide, dimethylaminomethyl-tbutyl peroxide, 1,1-di- (t-amylperoxy) cyclohexane , tamila peroxide, t-butylcumyl peroxide, t-butyl peroxide and / or 1-hydroxybutyl n-butyl peroxide.

Peresters and peroxycarbonates: butyl peracetate, cumila peracetate, cumila perpropionate, cyclohexyl peracetate, di-t-butyl peradipate, di-t-butyl perazelate, di-t-butyl perglutarate, dit- butyl, di-t-butyl persebacate, 4-nitrocumyl perpropionate, 1-phenylethyl perbenzoate, phenylethyl nitro-perbenzoate, phenylethyl nitro-perbenzoate, t-butylbicyclo- (2,2,1) heptane percarboxylate, t-perbutyrate -butyl-4-carbomethoxy, tbutylcyclobutane percarboxylate, t-butylcyclohexyl percarboxylate, t-butylcyclopentyl percarboxylate, tbutylcyclopropane percarboxylate, t-butyldimethyl percinnamate, t-butyl-2-butyl-2-butylbenzene diphenylate. , t-butyl-4-methoxy perbenzoate, t-butylperbenzoate, t-butylperoxyisoproprylcarbonate, t-butyl pertolate, percarboxylate

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57/69 t-butyl-l-phenylcyclopropyl, t-butyl-2-propylperpentene2-oate, t-butyl-l-methylcyclopropyl pefrcarboxylate, t-butyl-4-nitrophenyl peracetate, tbutilnitrophenyl peroxycarbamate, tcarbyl nitrophenyl peroxycarbamate butyl-N-succiimido, t-butyl percrotonate, t-butyl permaleic acid, t-butyl permethacrylate, t-butyl peroctoate, t-butyl peroxyisopropylcarbonate, t-butyl perisobutyrate, t-butyl peracrylate and / or t-butyl perpropionate;

Mixtures of one or more of the free radical forming agents listed above can also be used.

[0215] The compound (C), preferably one or more of the peroxides listed above, is present in a concentration of 0.3 to 4.0% by weight relative to the total amount of polymers A and B, typically between 0 , 5 and 3.0% by weight in relation to the total amount of polymers A and B.

[0216] Consequently, the impact-modified soft heterophasic propylene copolymer composition grafted in accordance with the present invention can be prepared by composing the components within suitable melt mixing devices to prepare polymeric compounds, including, in particular, extruders as single screw extruders, as well as twin screw extruders. Especially preferred are double-screw extruders, including kneading and mixing sections of high intensity. Suitable melting temperatures, i.e., average barrel temperatures, for preparing the compositions are in the range of 170 to 280 ° C, preferably in the range of 180 to 250 ° C.

[0217] The modification of reactive fusion or graft can, for example, be affected when dosing the components of

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58/69 polymer (A) and (B) separately in a double screw extruder such as Prism TSE24 40D with a temperature profile, such as 80/200/210/220/220/230/230/220/225/220 ° C and a screw speed of 200 to 500 rpm, preferably 250 to 400 rpm, more preferably, about 300 rpm (for example, 280 to 320 rpm). After heating and melting the polymer mixture, a solution of the thermally decomposing free radical forming agent, such as isopropyl tert-butylperoxy carbonate, preferably in acetone (10.0% by weight) is injected directly into the extruder.

[0218] The polymer melt / liquid / gas mixture is passed through the extruder, then, for intensive devolatization, discharged and pelleted.

Use

[0219] The invention is also directed to the use of the inventive composition of heterophasic propylene copolymer. Consequently, the present invention is directed to the use of the grafted heterophasic propylene copolymer composition to produce articles, such as extruded films or tubes, injection molded or blow molded articles, and to articles comprising the heterophasic propylene copolymer composition. grafted, preferably comprising more than 90.0% by weight of the impact modified heterophasic propylene copolymer composition, grafted.

[0220] Especially, such articles are medical tubes or bags that comprise more than 90.0% by weight of the grafted heterophasic propylene copolymer composition.

[0221] The invention will now be illustrated by way of

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59/69 reference to the following non-limiting examples.

Methods

The fraction soluble in xylene at room temperature (XCS,% by weight): The amount of the polymer soluble in xylene is determined at 25 ° C according to ISO 16152; 5th edition; 2005-07-01.

Intrinsic viscosity (IV)

[0222] The intrinsic (IV) viscosity value increases with the molecular weight of a polymer. The IV values, for example, of the XCS were measured according to ISO 1628/1 in decalin at 135 ° C.

The glass transition temperature Tg is determined by dynamic mechanical thermal analysis according to ISO 6721-7. Measurements are performed in torsion mode on samples molded by compression (40x10x1 mm3) between -100 ° C and + 150 ° C with a heating rate of 2 ° C / min and a frequency of 1 Hz.

MFR2 (230 ° C) is measured according to ISO 1133 (230 ° C, 2.16 kg load)

[0223] The melt flow rate is measured as MFR2 according to ISO 1133 15 (230 ° C, 2.16 kg of load) for polypropylene and according to ISO 1133 (190 ° C, 2.16 kg of load) for polyethylene and is indicated in g / 10 min. The MFR is an indication of the flow capacity and, consequently, the processing capacity of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.

[0224] The MFR2 of a fraction (B) produced in the presence of a fraction (A) is calculated using the measured values of MFR2 of fraction (A) and the mixture received after fraction production (B) (final):

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Log (MFRfinai) = fraction by weight (A) * Log (MFRa) + fraction by weight (B) ★ Log (MFRb,)

Comonomer determination by NMR spectrometry

[0225] Quantitative nuclear magnetic resonance (NMR) spectroscopy was also used to quantify the comonomer content and comonomer sequence distribution of the polymers. The quantitative ¹³ C { ¹ H} NMR spectra were recorded in the solution state using a Bruker Advance III 400 NMR spectrometer that operates at 400, 15 and 100, 62 MHz for ³ H and ¹³ C, respectively. All spectra were recorded using an optimized ¹³ C 10 mm temperature probe head extended to 125 ° C using nitrogen gas for all tires. Approximately 200 mg of material was dissolved in 3 ml of 1,2-tetrachloroethane-cfe (TCE-cfe) together with chromium- (111) -acetylacetonate (Cr (acac) 3) which results in a 65 mM solution of solvent relaxation (Singh, G., Kothari, A., Gupta, V., Polymer Testing 28 5 (2009), 475). To ensure a homogeneous solution, after preparing the initial sample in a hot block, the NMR tube was further heated in a rotating furnace for at least 1 hour. Upon insertion into the magnet, the tube was rotated at 10 Hz. This configuration was chosen primarily for high resolution and quantitatively necessary for accurate quantification of ethylene content. Standard single pulse excitation was used without NOE, using an optimized tip angle, 1 s recycle delay and a WALTZ16 double level decoupling scheme (Zhou, Z., Kuemmerle, R., Qiu, X ., Redwine, D., Cong, R., Taha, A., Baugh, D.

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Winniford, B., J. Mag. Reson. 187 (2007) 225; Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128). A total of 6,144 (6k) variables were acquired by spectra. The quantitative ¹³ C { ¹ H} NMR spectra were processed, integrated and relevant quantitative properties determined from the integrals using proprietary computer programs. All chemical shifts were indirectly referenced to the central methylene group of the ethylene block (EEE) at 30.00 ppm using the chemical solvent shift. This approach allowed comparable referencing even when this structural unit was not present. The characteristic signs that correspond to the incorporation of ethylene were observed in Cheng, Η. N., Macromolecules 17 (1984), 1950).

[0226] With characteristic signs corresponding to 2.1 erythro region defects observed (as described in L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev. 2000, 100 (4), 1253, in Cheng, Η. N., Macromolecules 1984, 17, 1950, and in WJ. Wang and S. Zhu, Macromolecules 2000, 33 1157) correction for the influence of region defects on certain properties was necessary. The characteristic signs that correspond to other types of region defects were not observed.

[0227] The comonomer fraction was quantified using the method of Wang et. al. (Wang, WJ., Zhu, S., Macromolecules 33 (2000), 1157) through the integration of multiple signals across the spectral region in the ¹³ C { ¹ H} spectra. This method was chosen because of its nature

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62/69 robust and ability to be responsible for the presence of region defects when necessary. The integral regions were slightly adjusted to increase the applicability throughout the range of comonomer content found. For systems in which only ethylene isolated in PPEPP sequences it was observed that the method of Wang et. al. has been modified to reduce the influence of non-zero integrals from locations that are known to not be present. This approach reduced overestimation of ethylene content for such systems and was achieved by reducing the number of sites used to determine the absolute ethylene content for:

E = 0.5 (3ββ + 3βγ + 3βδ + 0.5 (3αβ + Say))

[0228] Using this set of locations, the corresponding integral equation becomes:

E = 0.5 (Ih + Ig + 0.5 (Lc + Id)) using the same notation used in the article by Wang et. al. (Wang, W-J., Zhu, S., Macromolecules 33 (2000), 1157). The equations used for absolute propylene content have not been modified.

[0229] The comonomer incorporation in mole percent was calculated from the mole fraction:

E [mol%] = 100 * fE

[0230] The comonomer incorporation in weight percent was calculated from the mole fraction:

E [% by weight] = 100 * (fE * 28.06) / ((fE * 28.06) + ((1fE) * 42.08))

[0231] The comonomer sequence distribution at the triad level was determined using the method of analysis by Kakugo et al. (Kakugo, M., Naito, Y., Mizunuma, K.,

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Miyatake, T. Macromolecules 15 (1982) 1150). This method was chosen for its robust nature and slightly adjusted integration regions to increase applicability to a wide range of comonomer content.

Melting Temperature

[0232] The melting temperature (Tm) was measured with a Mettler TA820 differential scanning calorimetry (DSC) device on samples of 5 to 10 mg. DSC was performed according to ISO 3146 (part 3, method 02) in a cycle of 15 heat / cold / heat with a scan rate of 10 ° C / min in the temperature range from +23 to +210 ° C. The melting temperature was determined from the second heating step.

[0233] Tension modulus in the machine direction was determined according to ISO 527-1.2 at 23 ° C on 50 pm casting film produced on a monolayer melting film line with a melting temperature of 220 ° C and a cooling roll temperature of 20 ° C. The test was performed at a crossbar speed of 1 mm / min.

Styrene content

[0234] The styrene content is measured by Fourier transform infrared spectroscopy (FTIR). A 300 mm thick thin film is prepared from pelletized material by hot pressing (190 ° C, 100 bar, 1 minute). Two films are prepared per sample. Film samples prepared in this way are measured by a Perkin Elmer 2000FTIR IR Spectrophotometry System.

[0235] The peak at 1,602 cm-1 (Phenyl Absorption) is integrated and evaluated using a calibration curve

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64/69 internally established. The arithmetic medium of two measurements is provided as a result. Calibration: Several polypropylene compounds consisting of PP and an elastomer containing styrene (of known styrene content) are prepared and measured according to the method described above.

Charpy impact cut resistance

[0236] Charpy impact cut resistance (NIS) was measured according to ISO 179 leA at +23 ° C and -20 ° C, using 80x10x4 mm ³ injection molded bar test specimens prepared from according to EN ISO 1873-22.

[0237] Tension modulus in the machine direction was determined according to ISO 527-3 at 23 ° C on 50 pm casting film produced on a monolayer melting film line with a melting temperature of 220 ° C and a cooling roll temperature of 20 ° C. The test was performed at a crossbar speed of 1 mm / min.

F30 - Rheotens test

[0238] The test described in this document follows ISO 16790: 2005.

[0239] The filament hardening behavior is determined by the method as described in the article RheotensMastercurves and Drawability of Polymer Melts, Μ. Η. Wagner, Polymer Engineering and Sience, Vol. 36, pages 925 to 935. The content of the document is included for reference. The polymer filament hardening behavior is analyzed by a Rheotens apparatus (product of Göttfert, Siemensstr.2, 74711 Buchen, Germany) in which a fused filament is elongated by extraction with a defined acceleration.

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[0240] The Rheotens experiment simulates industrial extrusion and turning processes. In principle, a melt is pressed or extruded through a round matrix and the resulting filament is transported. The stress on the extrudate is recorded, as a function of melting properties and measurement parameters (especially the ratio of outlet speed and transport, practically a measure for the extension rate). For the results presented below, the materials were extruded with a HAAKE Polylab laboratory extruder system and a gear pump with cylindrical matrix (L / D = 6.0 / 2.0 mm). The gear pump was preset at a filament extrusion rate of 5 mm / s, and the melting temperature was set to 200 ° C. The length of the line of rotation between matrix and Rheotens wheels was 80 mm. At the beginning of the experiment, the admission speed of the Rheotens wheels was adjusted to the speed of the extruded polymer filament (zero tension force): Then, the experiment was started by slowly increasing the admission speed of the Rheotens wheels to the polymer filament itself. break up. The acceleration of the wheels was small enough that the tension force was measured under almost stable conditions. The acceleration of the extracted fused filament (2) is 120 mm / s2. The Rheotens was operated in combination with the PC EXTENS program. This is a real-time data acquisition program that displays and stores the measured data of tension strength and extraction speed. The risk parameters of the Rheotens curve (force versus rotating pulley speed) are taken as the melt resistance and extraction capacity values.

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Inventive Examples

[0241] The solid catalyst component was otherwise prepared according to Example 8 of WO 2004/029112, except that diethyl aluminum chloride was used as an aluminum compound instead of triethyl aluminum.

[0242] The catalyst obtained in this way was used together with triethyl aluminum (TEAL) as a cocatalyst and dicyclopentyl dimethoxy silane (D-Donor) as a donor to prepare the heterophasic polypropylene (A) copolymer used according to the present invention. The polymerization was carried out in a Borstar installation with a prepolymerization step, a cycle reactor and 2 gas phase reactors. The conditions can be seen in Table 1. The matrix was a random propylene copolymer, so a RAHECO was produced.

Table 1: Preparation of heterophasic polypropylene copolymer (A) with random copolymer as matrix, that is, RAHECO

RAHECO Prepolymerization TEAL / Ti [mol / mol] 210 TEAL / donor [mol / mol] 6, 95 Temperature [° C] 20 rep time [H] 0.38 Cycle Temperature [° C] 70 Pressure [kPa] 5,000 Division [%] 35

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RAHECO H2 / C3 ratio [mo 1 / kmo 1] 1.7 C2 / C3 ratio [mo 1 / kmo 1] 4.5 mf r ₂ [g / 1Omin] 8, 0 XCS [Weight %] 6, 5 C2 content [mol%] 3.7 GPR 1 Temperature [° C] 80 Pressure [kPa] 2,800 Division [%] 52 H2 / C3 ratio [mo 1 / kmo 1] 21.5 C2 / C3 ratio [mo 1 / kmo 1] 28.1 MFR ₂ (MFR _m ) [g / 1Omin] 8, 0 XCS [% by weight] 7.5 C2 content [mol%] 5, 9 GPR 2 Temperature [° C] 75 Pressure [kPa] 2,600 Division [%] 13 C2 / C3 ratio [mo 1 / kmo 1] 490 H2 / C2 ratio [mo 1 / kmo 1] 530 MFR ₂ (MFR _t ) [g / 1Omin] 7, 0 XCS [% by weight] 20, 0 IV (XCS) [dl / g] 1.5 C2 (XCS) [mol%] 40.3 C2 content [mol%] 11.5

C2 ethylene

H2 / C3 hydrogen ratio / propylene ratio

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C2 / C3

H2 / C2 ethylene ratio / propylene ratio hydrogen ratio / ethylene ratio

GPR 1/2 gas phase reactor

Cycle reactor

[0243] RAHECO was mixed in a twin screw extruder with 0.2% by weight of Irganox B225 (1: 1-mix of

Irganox

1010 (Pentaerythrityl-tetrakis (3- (3 ', 5'-diterc.butil-4-hydroxytoluyl) -propionate and tris (2,4-di-tbutylphenyl) phosphate) phosphite) from BASE AG, Germany) and 0.1 % by weight of calcium stearate.

[0244] In a next step, RAHECO (A) was mixed with 35.0% by weight of styrene-based elastomer (B).

[0245] The styrene-based elastomer (B) was VECTOR 4111 A, a styrene-isoprene-styrene block copolymer (STS) supplied by DEXCO.

[0246] This styrene-based elastomer (B) has, according to DEXCO, a styrene content of 18.0% by weight, an MFR ₅ 200 ° C of 12.0 g / 10 min and a Shore A ( ASTM D2240) of 40, density of 0.93 g / cm ³ .

[0247] The mixing was carried out in a cogiratory double screw extruder (Prism TSE24 40D) with a temperature profile of 80/200/210/220/220/230/230/220/225/220 ° C and a speed of 300 rpm screw. After heating and melting the polymer mixture (ie components (A) and (B)), a solution of the thermally decomposing free radical forming agent, ie, isopropyl tert-butylperoxy carbonate, in acetone, supplied by AkzoNobel was injected directly into the extruder.

[0248] The polymer melt / liquid / gas mixture is

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[0249] Subsequently, the polymer melt mixture was discharged and pelleted and grafted, impact-modified RAHECO compositions were produced. The properties of these compositions can be seen in Table 2.

[0250] CE1 is the pure base RAHECO produced according to Table 1.

[0251] CE2 is a fusion mixture of pure base RAHECO produced according to Tables 1 and 35, 0% by weight of styrene-based elastomer (B), again being VECTOR 4111 A, without the addition of POX.

Table 2:

unity CE1 CE2 IE1 IE2 IE3 RAHECO (A) % by weight 100 65 64.5 63.5 62.5 VECTOR 4111A % by weight 0 35 35 35 35 POX % by weight 0 0 0.5 1.5 2.5 MFRc g / 1Omin 8, 0 9, 5 2.8 2.4 8.7 XCSc % by weight 20, 0 46.8 41, 0 20, 8 14.4 XHI (gels) % by weight 0 0 0.45 1, 05 0.16 F30 cN n .m. 2, 6 5, 1 5, 2 5, 2 Voltage Module MPa 650 366 284 285 287 NTS -20 ° C kJ / m ² 1, 0 11.3 70, 8 71.3 71, 6 NTS -30 ° C kJ / m ² 2.2 5, 1 30, 0 n .m. 14, 8

MFRc MFR2 of composition

Composition XCScXCS

Claims (15)

1. Composition of grafted heterophasic propylene copolymer characterized by comprising (A) 30.0 to 95.0% by weight of a heterophasic polypropylene copolymer which has a melt flow rate (MFR 230 ° C / 2.16 kg, IS01133) from 0.1 to 100 g / 10min and comprising (al) a matrix (M) which is a homo- or copolymer of crystalline polypropylene and (a2) and elastomeric copolymer (E) dispersed in said matrix (M) and (B) 5.0 to 70.0% by weight of a styrene-based elastomer which is an unsaturated styrene block copolymer that contains at least one diene comonomer and has a styrene content of from 5.0 to 50.0% by weight measured by Fourier transform infrared spectroscopy (FTIR), and in which the styrene-based elastomer (B) is grafted onto the base heterophasic polypropylene copolymer (A). 2. Composition of heterophasic propylene copolymer, according to claim 1, characterized by the fact that the heterophasic polypropylene copolymer has a content of soluble cold xylene (XCS) determined according to ISO 16152 (25 ° C) in the range of 10 , 0 to 50.0% by weight, in which the content of cold soluble xylene (XCS) has an intrinsic viscosity (iV) determined according to DIN ISO 1628/1 (in decalin at 135 ° C) in the range of 1, 0 to 5.0 dl / g. Petition 870190101796, of 10/10/2019, p. 79/83 2/4 3. Composition of heterophasic propylene copolymer according to claim 1 or 2, characterized by the fact that the heterophasic polypropylene copolymer has a • total melt flow rate (MFRT) (ISO 1133; 230 ° C; 2.16 kg) in the range of 0.1 to 100.0 g / 10 min, • a total ethylene comonomer content, in polymerized form, in the range of 2.5 to 15.0% by weight, • a first glass transition temperature Tg (l) in the range of -12 ° C to +4 ° C and / or a second glass transition temperature Tg (2) in the range of -65 ° C to -30 ° C. 4. Composition of heterophasic propylene copolymer according to any one of the preceding claims, characterized in that the matrix (M) of the heterophasic polypropylene copolymer is a random propylene copolymer (R-PP) in which the propylene copolymer random (R-PP) has • an MFR2 melting flow rate (230 ° C) measured according to ISO 1133 in the range of 0.5 to 100.0 g / 10 min, and • an ethylene comonomer content and / or C4 to Cs a-olefins, in polymerized form, in the range of 1.0 to 12.0% by weight. 5. Composition of heterophasic propylene copolymer, according to any one of the preceding claims, characterized by the fact that both the random propylene copolymer (R-PP) and the elastomeric copolymer (E) are produced from propylene monomers and ethylene only. 6. Composition of heterophasic propylene copolymer, according to any of the preceding claims, characterized by the fact that the diene comonomer of the styrene-based elastomer (B) is selected from Petition 870190101796, of 10/10/2019, p. 80/83 3/4 butadiene and isoprene. 7. Composition of heterophasic propylene copolymer, according to any one of the preceding claims, characterized by the fact that the styrene-based elastomer (B) has a melting flow rate MFR2 (230 ° C, ISO 1133) at range of 2.0 to 200.0 g / 10min and • Shore hardness A measured according to ASTM D 2240 in the range of 25 to 65. 8. Heterophasic propylene copolymer composition according to any one of the preceding claims, the heterophasic propylene copolymer composition being characterized by having an MFR2 melting flow rate (230 ° C, ISO 1133) in the range of 0, 5 to 50.0 g / 10 min and • an insoluble hot xylene content in the range of 0.10 to 2.00% by weight. 9. Composition of heterophasic propylene copolymer, according to any one of the preceding claims, the composition of heterophasic propylene copolymer being characterized by having • a tension module according to ISO 527-1,2 measured in a casting film of 50 pm below 350 MPa and • Charpy impact cut resistance according to ISO 179 (leA) at -20 ° C of at least 15.0 kJ / m ² , and at 30 ° C of at least 7.0 kJ / m ² . 10. Process for producing the grafted heterophasic propylene copolymer composition as defined in any one of claims 1 to 9, the process being characterized by being a melt modification process Petition 870190101796, of 10/10/2019, p. 81/83 Reactive 4/4 comprising the stages of i) mixing component (A), the heterophasic polypropylene copolymer with component (B), the styrene-based elastomer and a thermal decomposition free radical forming compound (C) and ii) extruding said mixture. 11. Process according to claim 10, characterized by the fact that the heterophasic polypropylene copolymer (A) is produced in a multistage process comprising at least two reactors connected in series. 12. Process according to claim 10 or 11, characterized in that the thermal decomposition free radical-forming compound (C) is a peroxide. 13. Use of the grafted heterophasic polypropylene copolymer composition as defined in any of claims 1 to 9, characterized in that it is for producing articles selected from extruded films or tubes, bags, injection molded or blow molded articles. 14. Articles characterized by comprising more than 90% by weight of the grafted heterophasic polypropylene copolymer composition as defined in any one of claims 1 to 9. 15. Articles according to claim 14, the articles being characterized by being medical tubes or bags comprising more than 90% by weight of the grafted heterophasic polypropylene copolymer composition as defined in any one of claims 1 to 9.